METAL OXIDE pH SENSOR

Abstract

A pH sensor comprising a metal oxide-polymer composite, comprising: a continuous polymer resin matrix;, and a solid particulate, component dispersed in the polymer resin matrix comprising (i) metal oxides and (ii) a particulate carbon-based conductor wherein the metal oxides comprise Ta.sub.2O.sub.5 and RuO.sub.2 in a weight ratio of Ta.sub.2O.sub.5: RuO.sub.2 (on the basis of weight of metal component) in the range of from 90:10 to 10:90.

Claims

1. A pH sensor comprising a metal oxide-polymer composite, comprising: a continuous polymer resin matrix; and a solid particulate component dispersed in the polymer resin matrix comprising (i) metal oxides and (ii) a particulate carbon-based conductor wherein the metal oxides comprise Ta.sub.2O.sub.5 and RuO.sub.2 in a weight-ratio of Ta.sub.2O.sub.5:RuO.sub.2 (on the basis of weight of metal component) in the range of from 90:10 to 10:90.

2. A pH sensor according to claim 1 wherein the composite comprises a weight ratio Ta.sub.2O.sub.5:RuO.sub.2 (on the basis of weight of the metal component is in the range of from 70:30 to 30:70. 3. A pH sensor according to claim 1, wherein the metal oxide component of the composite comprises in the range of from 20% to 80% by weight of the total particulate solids comprising metal oxides and particulate conductor in the composite and the particulate conductor comprises from 20 to 80% by weight of the total particulate solids comprising metal oxides and particulate conductor.

4. A pH sensor according claim 1, wherein the particulate component comprising the metal oxides and particulate carbon-based conductor constitutes at least 40% by weight of the composite-composition.

5. A pH sensor according to claim 1, wherein the particulate component comprises in the range of from 60% to 80% by weight of the composite.

6. A pH sensor according to claim 1, wherein the particulate conductor is a particulate carbon-based conductor selected from particulate carbon, graphite, fullerenes, and carbon fibre.

7. A pH sensor according to claim 1, wherein Ta.sub.2O.sub.5 and RuO.sub.2 constitute at least 80% by weight of the total metal oxide content of the composite.

8. A pH sensor according to claim 1, wherein the-metal oxide component of the composite comprises further metal oxides in an amount of up to 20% by weight of the metal oxide component.

9. A pH sensor according to claim 8, wherein the metal oxide component further comprises one or more metal compounds selected from the group consisting of PtO.sub.2, IrO.sub.2,TiO.sub.2, Er.sub.2O.sub.3, ZrO.sub.2, Al.sub.2O.sub.3, RhO.sub.2, SnO.sub.2, La.sub.2O.sub.3, Li.sub.2O.

10. A pH sensor according to claim 1, wherein the particulate conductor is selected from the group consisting of particulate carbon and particulate graphite.

11. A pH sensor according to claim 1, wherein the particulate metal oxide is of particle size less than 100 microns.

12. A Ph sensor according to claim 1, wherein the polymer matrix is selected from the group consisting of polystyrene, polyurethane, acrylates, methacrylates vinyl resins, vinyl ester resin, phenol resin, epoxy resin, and mixtures thereof.

13. A pH sensor according to claim 1, wherein the metal oxide-polymer composite comprises: a polymer matrix in an amount of at least 15% by weight of the composite composition and dispersed in the matrix a mixture of particulate materials comprising: (i) particulate Ta.sub.2O.sub.5 in an amount, of at least 5% by weight (determined as Ta) of the composite composition; (ii) particulate RuO.sub.2 in at; amount of at least 5% by weight determined as Ru) of the composite composition; and (iii) particulate graphite in an amount of at least 5% by weight of the composition;, and optionally (iv) up to 5% by weight of other metal oxides selected from the group consisting of PtO.sub.2, IrO.sub.2,TiO.sub.2, Er.sub.2O.sub.3, ZrO.sub.2, Si.sub.3N.sub.4, Al.sub.2O.sub.3 and mixtures thereof.

14. A method of preparing a pH sensor comprising a metal oxide-polymer composite according claim 1, the method comprising dispersing a solid particulate component comprising metal oxides and carbon-based conductor in a hardenable liquid resin and hardening the liquid resin to form the polymer resin matrix, with dispersed solid particulate component wherein the metal oxides comprises Ta2O5 and RuO2 in a weight ration of Ta.sub.2O.sub.5:RuO.sub.2 in the range of from 90:10 to 10:90.

15. A method of preparing a pH sensor according to claim 14, wherein the polymer resin is an epoxy resin.

16. A pH sensor according to claim 1, further comprising a substrate to which the metal oxide-polymer composite has been applied.

17. A method of preparing a pH sensor according to claim 14, wherein the hardenable liquid resin comprising the dispersed solid particulate component is applied to a substrate by printing and hardened on the substrate.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0020] Embodiments of the invention are described with reference to the attached drawings. In the drawings:

[0021] FIG. 1 is a schematic cross section of a mixed metal oxide-polymer composite mounted on a wire and disposed within a ceramic tube to form a working pH sensor in accordance with an embodiment of the invention.

[0022] FIG. 2 is a schematic cross section of a pH sensor comprising a mixed metal oxide-polymer composite in accordance with an embodiment of the invention.

[0023] FIG. 3 is a schematic cross section of an pH sensor comprising a mixed metal oxide-polymer composite coating a conductive needle or fibre. The sensor of FIG. 3 may be used as a pH sensor of a biological sample in accordance with FIG. 4b showing the schematic representation of the pH sensor as an implant in a biological sample.

[0024] FIG. 4 is a graph comparing the slope of the mixed metal oxide composite pH sensor of an embodiment of single metal oxide sensors not of the invention referred to in the Example 5.

[0025] FIG. 5 is a graph showing the Intercept point of the calibration of the mixed metal oxide composite pH sensor of an embodiment and single metal oxide pH sensors not of the invention as referred to in the Examples.

DETAILED DESCRIPTION

[0026] The pH sensor comprises a metal oxide-polymer composite. The metal oxide-polymer composite comprises RuO.sub.2 and Ta.sub.2O.sub.5, and optionally also other metal oxides with a particulate carbon-based conductor dispersed in a polymer matrix. We have found that the pH sensing characteristics of the composite provide fast response times, are not sensitive to common cations and allow the use of economical fabrication methods. The composite also allows formation of miniature pH sensors and their use in a wide range of environments including industrial minerals processing, food processing, environmental monitoring and in biological systems.

[0027] The metal oxide component of the metal oxide-polymer composite includes RuO.sub.2 and Ta.sub.2O.sub.5 in a weight ratio of Ta.sub.2O.sub.5:RuO.sub.2 (based on metal component in the oxides) in the range of from 90:10 to 10:90, preferably from 80:20 to 20:80 and more preferably from 70:30 to 30:70. This presence of the RuO.sub.2 and Ta.sub.2O.sub.5 metal oxide particularly in these ratios provides an improvement in the sensitivity and resistance to interfering ion species which was not expected from the contribution of the respective metal oxides.

[0028] The metal oxide component of the metal oxide-polymer composite may include other metal oxides however in one set of embodiments it is generally preferred that the total of the RuO.sub.2 and Ta.sub.2O.sub.5 content constitute at least 70% by weight, preferably at least 80% by weight and most preferably at least 90% by weight of the total metal oxide content of the composite.

[0029] The metal oxide component of the composite may thus comprise further metal compounds such as one or more selected from the group consisting of PtO.sub.2, IrO.sub.2,TiO.sub.2, Er.sub.2O.sub.3, ZrO.sub.2, Si.sub.3N.sub.4, Al.sub.2O.sub.3 , RhO.sub.2, SnO.sub.2, La.sub.2O.sub.3 and Li.sub.2O.

[0030] The total amount of the metal oxides in addition to RuO.sub.2 and Ta.sub.2O.sub.5 is preferably in an amount of no more than 20% by weight, preferably from 5% to 20% of the total metal oxide component including RuO.sub.2 and Ta.sub.2O.sub.5.

[0031] The amount of Ta.sub.2O.sub.5 based on the total composite weight will depend on the sensitivity required, the ratio of RuO.sub.2:Ta.sub.2O.sub.5and nature and amount of other components such as the polymer and carbon based conductor. The particle size of the metal oxides may also have a bearing on the amount used. In one set of embodiments the amount of Ta.sub.2O.sub.5 (determined as Ta metal component) is at least 1% by weight of the composite composition, preferably at least 5% by weight. In certain embodiments the Ta.sub.2O.sub.5 content (based on Ta metal component) is in the range of from 1% to 25% by weight of the composite composition and more preferably in the range of from 5% to 25% such as 5% to 20% or 5% to 15% by weight of the composite composition,

[0032] The amount of RuO.sub.2 based on the total composite weight will depend on the sensitivity required, the ratio of RuO.sub.2:Ta.sub.2O.sub.5 and nature and amount of other components such as the polymer, carbon based conductor and any other metal oxides. The particle size of the metal oxides may also have a bearing on the amount used. In one set of embodiments the amount of RuO.sub.2 (determined as Ru metal component) is at least 1% by weight of the composite composition, preferably at least 5% by weight. In certain embodiments the RuO.sub.2 content (based on Ru metal component) is in the range of from 1% to 25% by weight of the composite composition and more preferably in the range of from 5% to 25% such as 5% to 20% or 5% to 15% by weight of the composite.

[0033] The particle size of the metal oxide has a bearing on the sensitivity and performance of the composite in monitoring pH. The optimum particle size may depend on the carbon-conductor content and the concentration of the components. In one set of embodiments the average particle size is less than 100 microns. We have found that particularly good results are generally achieved where the average particle size is less than 10 microns and particularly less than 5 microns. The value of using particles of particularly small size may be reduced by the cost of obtaining such particles. In one set of embodiments the particles are more than 20 nanometres, such as more than 50 nanometres or more than 100 nanometres in average size.

[0034] The solid particulate component dispersed in the polymer resin matrix comprises a carbon based conductor.

[0035] In one set of embodiments, the particulate component comprising the metal oxides and particulate carbon-based conductor constitute at least 40% by weight of the composite composition, preferably from 60% to 80% by weight of the composite composition.

[0036] The particulate carbon based conductor may be selected from a wide range of known carbon based conductors. Carbon based conductors may, for example, be selected from particulate carbon, graphite, fullerenes and carbon fibre.

[0037] The carbon based conductor may have a range of different morphologies depending on the nature and chemical structure of the carbon based conductor. The particulate carbon based conductor may comprise spherical particles, platelets, rods, fibres or combinations thereof and hence the particles may have non-uniform dimensions. In one set of embodiments the particle size is less than 100 microns such as less than 10 microns or less than 5 microns. In another embodiment the particles are elongated and of up to 1 mm in length such as up to 500 mm. The carbon-based conductor particles may, in the case of fibres, have a range of aspect ratios (maximum/minimum dimensions) such as aspect ratio of 1.5:1 to 20:1.

[0038] The more preferred carbon based conductor is selected from the group consisting of particulate carbon and particulate graphite.

[0039] In one set of embodiment the carbon based conductor comprises in the range of from 10 % to 70 % by weight of the composite composition and preferable in the range of from 15 % to 80 % by weight of the composite composition.

[0040] The particulate component including the metal oxides and carbon based conductor are dispersed in a polymer resin matrix.

[0041] The polymer matrix may be selected from a wide range of suitable resins. The resin will generally be resistant to a range of pH conditions. Suitable polymer resins may be selected from the group consisting of, polystyrene, polyurethane, polyolefins (such as polyethylene, polypropylene and polyolefin blends), acrylates, methacrylates, vinyl resins, vinyl ester resin, phenol resin, epoxy resin and mixtures thereof.

[0042] In one set of preferred embodiments the pH sensor comprises a metal oxide-polymer composite which comprises: [0043] a polymer matrix in an amount of at least 15% by weight of the composite composition and dispersed in the matrix a mixture of particulate materials comprising: [0044] (i) particulate Ta.sub.2O.sub.5 in an amount of at least 5% by weight (determined as Ta) of the composite composition; [0045] (ii) particulate RuO.sub.2 in an amount of at least 5% by weight (determined as Ta) of the composite composition; and [0046] (iii) particulate graphite in an amount of at least 5% by weight of the composition; and optionally [0047] (iv) up to 5% by weight of other metal oxides selected from the group consisting of PtO.sub.2, IrO.sub.2,TiO.sub.2, Er.sub.2O.sub.3, ZrO.sub.2, Si.sub.3N.sub.4, Al.sub.2O.sub.3 and mixtures thereof.

[0048] In a preferred set of embodiments the composite comprises: [0049] a polymer matrix in an amount of from 15% to 80% (more preferably 20% to 50%) by weight of the composite composition and dispersed in the matrix a mixture of particulate materials comprising: [0050] (i) Ta.sub.2O.sub.5 in an amount (based on Ta metal component) of from 5% to 25% such as 5% to 20% or 5% to 15% by weight of the composite; [0051] (ii) RuO.sub.2 an amount (based on Ru metal component) in the range of from 5% to 25% such as 5% to 20% or 5% to 15% by weight of the composite; [0052] (iii) carbon based conductor in an amount in the range of from 10 % to 70% by weight of the composite composition and preferable in the range of from 15% to 60% by weight of the composite composition; and [0053] (iv) 0% to 5% by weight of other metal oxides selected from the group consisting of PtO2, IrO2, TiO2, Er2O3, ZrO2, Si3N4, Al2O3 and mixtures thereof.

[0054] In a further set of embodiments there is provided a pH sensor comprising the composite as hereinbefore described provided on a conductive substrate for connection to a circuit for measuring potential change attributable to pH change. The conductive substrate may be a metal wire, rod, fibre, strip sheet or the like and the composite of the invention lends itself to being used in a range of applications and structures. The circuit may include a reference electrode of well known type.

[0055] One of the advantages of the composite for use as a pH sensor is that it may be formed in a wide range of shapes and forms to provide pH sensors designed for specific applications.

[0056] The metal oxide-polymer composite may be formed using a liquid resin which allows the particulate materials to be dispersed in the liquid resin and the liquid resin transformed to a hardened state. This allows the composite to be incorporated into a moulded structure, applied as a coating to a suitable substrate or printed onto a suitable substrate. Suitable substrates may be conductive such as metals which may form part of a signal processing circuit. Alternatively, the substrate may simply provide a support for the composite and be conducting or non-conducting with a separate conducting connection being provided to the composite for signal processing.

[0057] In one embodiment the polymer resin is a thermoplastic and the particulate materials are incorporated into the resin matrix while the resin is in a thermally induced plastic state. For example the polymer resin of thermoplastic type may be plasticized and blended in the plasticized state with the particulate materials, In a further example a thermoplastic polymer in particulate form may be mixed with the particulate metal oxide and carbon based conductor and moulded with application of heat to fuse the resin with the particulate metal oxide and carbon based conductor dispersed therein. The resins prepared by thermal processing can include, but not be limited to, such resin materials as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polyethers and polyvinylidene fluoride.

[0058] In another set of embodiments the polymer resin and particulate material is dispersed in a suitable liquid medium and a solid composite is produced by co-deposition or removal of the solvent. For example PVC may be dispersed in a solvent, such as DMF, allowing co-dispersion of the particulate materials and the composite produced by separation of the composite from the solvent (for example by addition of water where the solvent is DMF).

[0059] In another embodiment the liquid resin is a liquid polymerizable composition which can be hardened by polymerization to form the polymer resin. The precursor may comprise one or more monomers or prepolymers in which the particulate materials are dispersed prior to curing to form the polymer resin matrix. Curing may be carried out by a wide range of polymerization processes known in the art for forming different polymers such as thermosets, polymerisation catalysts, UV curable compositions and the like. The hardenable resin can be a phenol-formaldehyde resin, a phenol-furfural resin may for example be bisphenol epoxy resin, a halogenated bisphenol epoxy resin, a peracteic acid oxidized polyolefsn epoxy resin, a methyacrylate resin, an acrylaie resin, epoxy resin or any combination thereof.

[0060] In one embodiment the polymer resin is formed from a hardenable liquid resin and a hardening catalyst, these components preferably being stored separately until the resin is required to set hard. When the components are mixed the resin hardens by a process of cross-linking and/or polymerisation. The liquid resin and hardening catalyst may be mixed together before mixing with the particulate material or mixing with the liquid resin and particulates to be carried out prior to addition of the hardening catalyst. The appropriate order of mixing may depend on the speed of hardening with the chosen components and reaction conditions. One preferred example is a liquid epoxy resin and amine based hardening catalyst.

[0061] The pH sensor may comprise the composite formed about a substrate or as a coating or printed structure on a substrate. In one set of embodiments the resin is applied in liquid form to a substrate such as a wire, rod, fiber, sheet or the like and hardened. The liquid resin may be applied to a surface by coating or by printing and hardened to form the polymer resin matrix.

[0062] We have found that pH sensors of mixed Ta.sub.2O.sub.5 and RuO.sub.2 metal oxides with graphite powders and polymer resin to form metal oxide composites show linear Nernstian response between pH 1-12 with the slope of 40-60 mV/pH unit.

[0063] The pH sensor shows robust resistance to acid, high temperature and pressure making it suitable for use in a wide range of applications in the food processing, industrial chemistry, research and minerals processing in which conventional pH electrodes are not able to operate. The sensor may also be produced at a relatively low cost compared with conventional electrodes. A significant advantage of the pH sensor is in the ability to vary the dimensions, shape and supporting substrate used in fabrication of the pH sensor. The composite may be moulded to a variety of shapes or can be applied by a wide range of coating and printing techniques making the technology much more amenable to different uses and applications.

[0064] There is also a very significant improvement from reduced interference in the pH sensor compared with similar metal oxide based pH sensors. Indeed, the presence of both ruthenium and tantalum oxides in the required ratio significantly reduces interference from ions commonly present in environments where pH monitoring is required.

[0065] Examples of pH sensors will be described with reference to the attached drawings.

[0066] FIG. 1 shows a simple pH working sensor (100) in accordance with an embodiment of the invention which comprises a pH sensing composite in accordance with the invention (110) which is connected at a connection point (120) to a wire (130) for connection to a circuit for measuring potential change attributable to pH change. The pH sensor may further comprise a protector (140) for protecting the composite and connection (120). The protector (140) may be formed of a suitable plastics material.

[0067] FIG. 2 shows a pH sensor (200) in accordance with a further embodiment of the invention which is adapted for use in the corrosive environment such as an acid leach mineral recovery process. An electrode portion (210) is connected at connection point (220) to a wire (230) for connection to a circuit for measuring potential change attributable to pH change. The electrode (210) is formed of an elongate conductive metal substrate such as a metal rod or strip and which has a coating of pH sensing composite (250) in accordance with the invention at the operational end (260) remote from connection point (220). The pH sensor (300) is provided with a protector (270) in the form of a plastic shell extending about the composite coated portion (250) of the sensor and comprises a membrane (280) at the operational end (280) allowing ingress of liquid subject for pH determination for contact with the composite (250).

[0068] FIG. 3a and 3b show a pH sensor (300) for use in determining the pH of a biological material (310) in which it may be implanted as shown in FIG. 3b. The pH sensor has an electrode portion comprising a conductive needle or fiber (320) provided with a coating of pH sensing composite (330) in accordance with the invention. The electrode conductive portion (320) is connected at connection point (340) to a wire (350) for connection to a circuit for measuring potential change attributable to pH change. The operative portion of the electrode may be protected by a membrane (360) which allows the ingress of liquid subject to pH determination from the biological material (310). The pH sensor of this embodiment may be fabricated in a very small size such as 100 microns to 1 mm in size and in a range of shapes.

[0069] The invention will now be described with reference to the following examples. It is to be understood that the examples are provided by way of illustration of the invention and that they are in no way limiting to the scope of the invention.

EXAMPLES

Examples 1 to 3 and Comparative Examples 4 and 5

[0070] Composites and electrodes of these examples were prepared using the general method described below to prepare electrode with composited shown in Table 1.

Preparing a Mixed Metal Oxide-Polymer Composite Electrode:

[0071] 1. Epoxy Polymer resin (bisphenol-A-epichlorhydrin) is mixed with curing agent (3-aminomethyl-3,5,5-trimethylcyclohexylamine) just before the preparation of the electrode. [0072] 2. Metal oxide powders (particle size <5 μm), graphite (particle size <20 μm) and polymer are weighed. [0073] 3. Metal oxide powders and graphite are mixed together (and possibly grinded) for 2-5 minutes to prepare a homogeneous powder. Additional metal oxides such as lanthanum (III) oxide, lithium oxide and mixtures thereof may be used in a total amount of up to 5% by weight if desired. [0074] 4. Polymer is mixed thoroughly with graphite-metal oxide powder in a jar (low consistency) or with mortar and pestle (high consistency) for 2-5 minutes. [0075] 5. Paste or suspension is formed into the shape of an electrode for example by: [0076] a. Pressing the paste inside a plastic tube (FIG. 1) [0077] b. Printing the composite on a conductive substrate (FIG. 2) [0078] c. Dip-coating composite on a conductive fiber (FIG. 3) [0079] 6. Mixed metal oxide-polymer composite is cured in oven at 60° C. for 2-4 hours and possibly polished with 1200 grit sandpaper. [0080] 7. In order to prevent the interference of some ions and redox-active species on sensor signal, protective membrane (nafion, polyurethane etc.) can be coated on top of the sensing material. [0081] 8. Sensor and reference electrode, e.g. Ag/AgCl (3 M KCl), are connected into a potential logging device. [0082] 9. Sensor is calibrated by recording potential values of the sensor in pH buffer solutions, e.g. pH 4, pH 7 and pH 10.

TABLE-US-00001 TABLE 1 Examples of the composition of the mixed metal oxide sensors and single metal oxide sensors. Example Polymer Graphite Ta2O5 RuO.sub.2 *3H.sub.2O 1 40.4 17.9 10.5 31.2 2 39.9 30.1 15.0 15.1 3 30.1 35.1 8.6 26.2 CE4 40.8 29.7 0.0 29.5 CE5 40.0 30.1 29.9 0.0 [0083] Sensitivity of the mixed metal oxide electrodes to protons (pH) was higher than pure metal oxide composite electrodes of Comparative Examples 4 and 5 (CE4 and CE5). [0084] Hysteresis of the slope was smaller for the mixed metal oxide electrodes compared to the pure metal oxide electrodes (difference between acid to base and base to acid slopes), [0085] Intercept (mV at pH 0) point was more stable for the mixed metal oxide sensors.

TABLE-US-00002 TABLE 2 Slope and intercept of the composite electrode and difference of sensor signal measured from acidic pH towards basic pH and vica versa. Slope (mV/pH unit) Intercept (mV) Acid to Base to Acid to Base to Example base acid Diff. base acid Diff. Day 1 1 −58.6 −57.3 −1.3 694.9 678.4 16.5 2 −57.6 −58.0 0.4 657.2 661.7 −4.5 3 −58.9 −58.2 −0.7 697.9 685.6 12.3 CE4 −54.1 −51.7 −2.4 672.4 641.7 30.7 CE5 −45.6 −28.8 −16.8 412.9 274.9 138.0 Day 7 1 −55.5 −56.1 0.6 607.5 604.4 3.1 2 −56.6 −56.5 −0.1 592.5 584.1 8.4 3 −57.5 −57.6 0.1 609.3 605.2 4.1 CE4 −44.5 −45.4 0.9 532.7 519.8 12.9 CE5 −42.2 −29.3 −12.9 370.2 261.8 108.4

[0086] FIG. 4 shows a plot of the slope of the ph sensors of Example (ex) 3 and Comparative Examples (CE) 4 and 5. [0087] Slope of the mixed metal oxide sensor stabilised during the first 2 days (stored in pH 7 buffer). Mixed metal oxide sensor maintained high sensitivity to protons for several weeks whereas pure metal oxide sensors suffered significant loss of sensitivity (−10 mV/pH or more). [0088] Intercept point of the calibration slope stabilised during the first 2 days of storage (pH 7 buffer).

[0089] FIG. 5 shows the intercept point of the calibration of the mixed metal oxide composite sensor (Ex 3) and single metal oxide sensors (CE4 and CE5). [0090] Mixed metal oxide sensors were less sensitive to chlorides than pure metal oxide sensors.

TABLE-US-00003 TABLE 3 Interference caused by the Cl.sup.− anions and difference of the measured pH between a commercial and mixed metal oxide composite electrode. Example 1 CE4 CE5 Measured pH Cl.sup.− 0.03M 6.957924 6.943846 6.996631 Cl.sup.− 0.3M 6.778634 6.707098 6.745546 Cl.sup.− 0.6M 6.697703 6.594617 6.482754 Difference between sensors Cl.sup.− 0.03M −0.00308 −0.01715 0.035631 Cl.sup.− 0.3M −0.01037 −0.0819 −0.04345 Cl.sup.− 0.6M −0.0133 −0.11638 −0.22825